Hair treatment compositions containing polycondensable compounds

ABSTRACT

A composition for treating hair containing a cosmetically effective amount of a polycondensable compound having the formula:   IN WHICH: Y is selected from the group consisting of H, hydrocarbon chains comprising one to 30 carbon atoms, groups consisting of cosmetic constituents which have -S-S, -SH, -COOH, basic quaternary ammonium, and fatty chain groups, X is selected from the group consisting of O, S and NH, R1 and R2 are selected from the group consisting of lower alkyl and together may form a heterocyclic group, comprising nitrogen and/or oxygen atoms, R3 is selected from the group consisting of H, alkyl, and the two R3 groups may form a heterocyclic group, comprising nitrogen and/or oxygen atoms.

United States Patent Kalopissis et a1.

[ July 18,1972

Abegg, Le Perreux; Gulliana Ghilardi; Henri Philippe De Beaulieu, bothof Paris,

all of France [73] Assignee: Societe anonyme dite: LOreal [22] Filed:Oct. 23, 1968 [21] Appl.No.: 770,074

[52] US. Cl ..424/7l, 8/l27'.51, 8/127.6, 132/7, 260/246 B, 260/247.l,260/247.2 A, 260/295 E, 260/295 G, 424/47, 424/70 [51] Int. Cl. A6lk7/10 [58] Field of Search ..260/246, 247.1, 247.2, 247.2 A, 260/553 R;424/70, 71, 72; 8/116.2, 116.3, 127.51, 127.6

[56] References Cited UNITED STATES PATENTS 2,203,493 6/1940 Evans eta]... ..8/1 16.3 2,203,504 6/1940 Piggott et al. ....260/553 X 2,203,5056/1940 Piggott et a1. ....260/553 X 2,203,506 6/1940 Piggott et a1.....260/553 X 2,220,508 11/1940 Bock et a1 ....260/553 X 2,340,046 1]1944 DAlelio ....260/553 X 3,065,110 11/1962 l-lagge et a1. ..260/553 X3,310,539 3/1967 Convert et a]. 260/246 X 3,098,693 7/1963 Sheehan..424/7l X Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C.Clarke Attorney-Holcombe, Wetherill & Brisebois [5 7] ABSTRACT Acomposition for treating hair containing a cosmetically effective amountof a polycondensable compound having the formula:

in which:

Y is selected from the group consisting of H, hydrocarbon chainscomprising one to 30 carbon atoms, groups consisting of cosmeticconstituents which have SS, --SH, -C0Ol-l, basic quaternary ammonium,and fatty chain groups,

X is selected from the group consisting of O, S and NH,

R and R are selected from the group consisting of lower alkyl andtogether may form a heterocyclic group, comprising nitrogen and/oroxygen atoms,

R,, is selected from the group consisting of H, alkyl, and the two Rgroups may form a heterocyclic group, comprising nitrogen and/or oxygenatoms.

4 Claims, No Drawings I-IAIR TREATMENT COMPOSITIONS CONTAININGPOLYCONDENSABLE COMPOUNDS SPECIFICATION This invention relates to acosmetic composition for improving the condition of human hair andimparting thereto properties which are advantageous when the hair is tobe subsequently subjected to a cosmetic treatment.

It is known that the hair is more or less degraded by the action ofatmospheric agents such as the sun and sea water, and by chemicaltreatments to which it is subjected, for example, during permanentwaving and bleaching.

The effects of such degradation may be to a large extent eliminated byusing the compositions according to the present invention.

It has already been proposed that the strength and elasticity of thehair be increased by treating it with compounds which may be polymerizedinside the keratinic fiber, and at the same time become attached to thereactive groups of the keratin.

Among the compounds heretofore suggested for this purpose aredimethylolurea and dimethylolthiourea, which have, however, thedisadvantage of causing the release of a substantial quantity of freeformol, the presence of which in contact with the scalp cannot betolerated.

It has also been suggested that compounds which are more stable thandimethylolurea and dimethylolthiourea, that is to say, compounds whichrelease much less free forrnol be used for this purpose.

However, these compounds have in common the characteristic of comprisinghydroxymethyl groups which prevent them from being completely stable.Moreover, these products are difficult to prepare in a very pure state,from which it follows that the process of preparing them do not lead torigorously reproducible results.

On the other hand, a great many of these compounds are difficult todissolve in the aqueous solvents generally used in the cosmetic field.

In order to at least partially eliminate these disadvantages, it hasbeen suggested that one might use, instead of the hydroxymethylderivatives themselves, particular derivatives of these compoundsobtained in a known manner by condensing them with secondary amines inaccordance with the Mannich reaction.

The compounds produced in accordance with this reaction are moresoluble, more stable, and easier to prepare than the correspondinghydroxymethyl compounds and are thus appreciably more satisfactory whenused for the cosmetic purpose of strengthening the hair.

On the other hand, this method of treating the keratin of the hair alsoseeks to introduce into the hair reactive groups having a particularcosmetic value, at the same time that it strengthens the hair.

Specifically, cosmetic compounds having disulfide bonds have beenchemically attached to the hair. This supplement to the SS bondsimproves the behavior of the hair and affects the action of the fiberwith respect to the chemical reactants customarily used in the cosmeticfield, such as reducing solutions containing mercaptans or sulfites, oroxidizing agents containing hydrogen peroxide, for example.

In like manner cosmetic compounds having carboxylic groups have beenattached inside the hair. These additional acid groups greatly increasethe affinity of the fiber for basic dyes.

On the other hand, basic groups, or even fatty chains, have beenintroduced into the hair in order to increase the afiinity of the hairfor acid dyes, or improve the sheen and feel of the hair over asubstantial period of time.

It has now been discovered that these difierent purposes may be servedby using compounds having in their molecule both a function capable ofcausing polycondensation and a second function serving the othercosmetic purposes outlined above. In this manner, when this type ofproduct is polycondensed in a conventional manner inside the keratin,the result in which:

Y is selected from the group consisting of H, hydrocarbon chainscomprising one to carbon atoms, groups consisting of cosmeticconstituents which have SS-, Sl-l, COOl-l, basic quaternary ammonium,and fatty chain groups,

X represents oxygen, sulfur, or --Nl-l,

R and R represent lower alkyl groups and may form part of a heterocyclicring,

R represents a hydrogen atom or an alkyl radical, and the two R groupsmay be connected together to form a heterocyclic ring comprisingnitrogen and/or oxygen atoms.

In one particular embodiment of the invention, the composition fortreating or modifying the keratin of the hair comprises at least onepolycondensable compound corresponding to the formula:

R: X R: R2 ill) R1 --(lIlr-N Among the polycondcmnhhcompound which mayllc uscd in thc composition according to tho invcntionmonomorpholinomethyluruu, having the formula:

dimorpholinomethylureu, lmving the formula:

l. A composition for treating human hair comprising a solution in asolventsclcctctl from tho group consisting of water and hydroalcoholicsolutions, of 0.5 to 12% by weight of a polycolldcnsztbhcompoundselected from the group consisting of morpholinomcthylurea quatcrnizcdwith methyl iodidc and 75 methcxymethylut'eidorncthyl pyridiniulnchloride.

2. A composition according to claim which also contains an acid catalystselected from the group consisting of acetic acid, lactic acid,phosphoric acid, monosodium phosphate and monopotassium phosphate,

dimorpholinoniethylthiinu'ea, having the formula:

monoinorpholinomethylthiourca, having the formula:

/ O NCH2-NH-CNH2 monomorpholinomethylethyleneurea, having the formula:

CHT-NH 1,4-bis(carhainidomethyl)pipcrazinc, having the formula'diethylaminomethylurea, having the formula:

piperidinomethylurea, having the formula:

CH -CH; Cg NCHgNH --(f -Nll- CH2 OHg H In one embodiment, thecomposition according to the invention comprises a group having theformula:

in which:

X, R, R R and Y have the significances set forth in formulas I and II,

R, represents an alkyl radical or a radical having a function orchemical bond imparting a cationic property to the nitrogen and,

A represents an anion of the halide or sulfate type.

Among the polycondensable compounds of this type which may be used inthe composition according to the invention are:

morpholinomethylurea quatgmized with methyl iodide having the formula:

methoxymethylin'eidinnclhyl pyridininni chloride having the formula:

In a preferred embodiment of the invention the group according to theabove formula I is attached to a group having a chemical function whichis especially reactive with respect to conventional cosmetic reagents,which group is hereinafter referred to as the cosmetic constituent andcorresponds to group R in formula I].

Among the cosmetic constituents suitable for use in carrying out thepresent invention are those groups having a disulfide function, a thiolfunction, a carboxylic acid function, a basic or quaternary ammoniumfunction, or a fatty chain.

Among the cosmetic constituents which may be used in compositionsaccording to the invention are:

(N-carbamyl-N'-morpholinomethylcarbamyl)cystamine, having the formula:

i .\-(Jll:(flIzNll-C (J-Nll:

N,N(morpholinorncthylcarlmmyl)rystinnine, having tlnformula:

N (inorpholii\onu-tllylczn'lnnnyl)cystinninc, having the forinnln:

(methyl-propylurea-N-(mor;)hollnomcthyl)propylurcunmlnc, having theformula:

methyl dl-lN-(morphollnomethyl)propylureahminc having the formula:

(N-dimethyl-ethylurcu-N llmethyl-morpholinoniethylurcldoethyl) havingthe formula:

N =dodecyl-N-(morpholinomethyl) urea In a preferred embodiment of theinvention the cosmetic compositions are in the form of aqueous orhydroalcoholic solutions containing 0.5 to 12 percent by weight andpreferably 2 to 4 percent by weight of at least one polycondensablecompound such as has been hereinbefore described. These cosmeticcompositions may have a pH of 1.5 to 10.

The cosmetic compositions according to the invention may also contain anacid catalyst which may be either a mineral or an organic acid, such asphosphoric acid, acetic acid, etc, or an acid reaction salt such asmonosodium and monopotassium phosphate capable of promoting thepolycondensation of these compounds with the keratinic fiber whenheated.

The cosmetic compositions according to the invention may also containnitrogenous compounds of the urea family and in particular ureins, whichmay have cosmetic constituents of the type defined above attached totheir nitrogen atoms.

Such ureins can correspond to the following formula in which X isselected from the group. consisting of O, S, NH, n l or 2 Y is achemical group which has cosmetic properties selected from the groupconsisting of disulfide, carboxylic acid, tertiary amine, quaternaryamine, fatty chain and SI-I groups.

The composition may also take the form of a gel, cream, or aerosol. Itmay also contain any conventional cosmetic additives, such assurface-active agents, penetrating agents, perfumes, resins, etc.

In accordance with the invention, the cosmetic composition may bepackaged in two phases destined to be mixed at the moment of use on thehair, one phase being solid and containing the polycondensable compoundsand the other phase being aqueous or hydroalcoholic and containing theacid catalyst and any conventional cosmetic additives.

In particular, the solid or aqueous phase of the cosmetic compositionpackaged in this manner may also contain a salt of sulfurous acid, suchas sodium metabisulfite.

A further object of the present invention is to provide a new processfor treating hair characterized by the fact that the hair is impregnatedwith the above composition, and dried by the application of heat,possibly after having been rinsed.

In a first method of carrying out this process, the cosmetic compositiondoes not itselfcontain the acid catalyst necessary to causepolycondensation of the polycondensable compounds in the keratinicfiber, and this acid catalyst is instead applied directly to the haireither before or after applying the composition according to theinvention.

In another method of carrying out this .process, a cosmetic compositionwhich does contain the acid catalyst is applied directly to the hair,which is then dried as previously described.

The treatment according to the invention makes it possible tosubstantially strengthen the keratinic fiber of the hair by forming apolycondensate inside the hair which also becomes attached to thereactive groups of the keratin. In this manner it makes it possible to'obtain sets of excellent quality when the hair is treated while woundup on setting rollers.

On the other hand, when the polycondensable compounds also comprisecosmetic constituents, the treatment according to the invention alsomakes it possible to carry out subsequent cosmetic treatments, such asbleaching, dyeing, permanent waving, etc., under greatly improvedconditions.

It is a further object of the present invention to provide, as a newarticle of manufacture, compounds corresponding to the formula:

in which X, R,, R R are as defined above, and

R, represents a cosmetic constituent as hereinbefore defined.

The present invention comprises, in particular, the following newcompounds: N-(carbamyl-N-morpholinomethylearbamyl)cystamine,

N ,N'-(morpholinomethylcarbamyl)cystamine, N-morpholinomethylcarbamyl)cysteamine, N- (morpholinomethylcarbamylglycine, (diethyl-methyl- 'rnorpholinomethyl-ureidoethyl) ammoniumiodide,

(dimethyl-copra-morphoIinomethyl-ureidoethyl) ammonium chloride,[N-(morpholinomethyl) ethylurea-diethyl-ethylurea]ammonium chloride,methyldi-[N- (morpholinomethyl)propylureahamine, methyldi-[N-(morpholinomethyl) propylurea1arnine, and(N-dimethylethylurea-N-dimethyl-morpholinomethyl ureidoethyl) cystaminedichloride, the formulas for which compounds have been given above.

It is also an object of the present invention to provide a process forpreparing the above-described new compounds, which process ischaracterized by the fact that, in a first step, a urein is preparedwhich contains the cosmetic constituent defined above by reacting acyanate or an alkaline thiocyanate with a primary amino hydrochloride sothat the nitrogen of the amine becomes attached to the cosmeticconstituent.

In a second step, a reaction of the Mannich" type such as described inOrganic Reactions" vol. 1, ch. 10, p. 303 and I-Iouban Weyl XIV/2, pp.342-354 is carried out by reacting the urein which has thus been formedwith a secondary amine in the presence of formol, the reaction beingcarried out in aqueous solution, either at room temperature or at atemperature of about 50 to 60C.

In an alternative process according to the present invention a tertiaryamine is quaternized with a halogeno-ethylurea, so that the nitrogen ofthe amine becomes attached to a cosmetic constituent.

In a second step in this alternative process the urein compound obtainedin the first step is reacted with a secondary amine in the presence offormol, as hereinbefore described.

In order that the invention may be better understood, several exampleswill now be described, purely by way of illustration.

EXAMPLES OF PREPARATION 1. Preparation of dimorpholinomethylthiourea 1mol of thiourea is dissolved in two mols of formol in an aqueous 30percent solution, at a temperature of 40-50C.

This is cooled below 20C and 2 mols of morpholine are added slowly whilekeeping the temperature between l5-and 20C. This is then cooled to l0Cuntil the dimorpholinomethylthiourea crystallizes out. (This takes atleast 24 hours.)

1 mol of N,N-dicarbamyl-cystamine, 1 mol of formol in an aqueous 30percent solution, 1 mol of morpholine and 500 cc of distilled water aremixed while stirring.

The resulting reaction is exothermic but it is nevertheless necessary toheat the mixture to 50-55C to dissolve the reagents. The mixture is thenpermitted to revert to the ambient temperature and cooled to l 5C. Thereaction product solidifies, and is dried under vacuum on P It is awhite crystalline product. The yield of the reaction is better than 90percent.

Total amines 3.0 meq/g Theoretical 2.96 meq/g Tertiary amines 2.7 meq/gTheoretical 2.96 meq/g 3. PreparationN,N'-(morpholinomethylcarbamyl)cystamine.

4. Preparation of (dimethyl-copra-morpholino-methylureidoethyl) ammoniumchloride.

CH1 (0pm j cm (Cll:):NllC0Nll(.ll:N 0

1 mol of (dimethyl-copra-ureidoethyl) ammonium chloride, prepared byquaternization of dimethyl-copra with chloroethylurea, is dissolved indistilled water. 1 mol of formol in an aqueous 30 percent solution isthen added. Morpholine is then added slowly, while stirring. Thereaction is exothermic. The temperature is kept near 50C. When thetemperature falls, the reaction mixture is evaporated until dry. This isredissolved by heating it in 2,400 cc of ethanol, and the mixture isthen again evaporated until dry. The resulting product is a yellow oil,which after mixing with ether and vacuum drying, forms a translucentlighbcolored paste. The yield of the reaction is 87 percent.

1 mol of N-methyl-dipropylurea, 2 mols of formol in an aqueous 30percent solution, and 2 mols of morpholine are mixed while stirring, andthen heated for 30 minutes at 50C. The reaction mixture is evaporateduntil dry, and after washing several times with ether and vacuum dryingon P 0 the result is a white crystalline product.

The yield of the reaction is 82.5%.

Total amines 6.57 meq/g Theoretical 7.0 meq/g Tertiary amines 6.32 meq/gTheoretical 7.0 meq/g EXAMPLES OF APPLICATION EXAMPLE I:

A head of hair is first bleached with a conventional oxidizingcomposition, rinsed, and dried. The hair is then impregnated with thefollowing solution:

monomorpholinomethylthiourea 2 g polyvinylpyrrolidone/vinyl acetatecopolymer 0.4 g acetic acid, q.s.p. pH=2.8

water, q.s.p. I00 cc A head of hair is then set and dried under a hoodfor 30 to 40 minutes at a temperature of about 4550C. The hair ismarkedly hardened and is easily arranged. The tips of the hair appear tobe in good condition. The set is springy, and lasts well.

EXAMPLE ll:

A solution having the following composition is applied to natural hairwhich has first been washed and dried:

l,4-bis(carbamidomethyl )piperazine water The hair is then wound up onsetting rollers and carefully impregnated with a 2 percent lactic acidsolution. The hair is left to dry under a hood at about 45C and a set ofexcellent quality results.

EXAMPLE III:

Hair which has been strongly bleached is impregnated with a solutionobtained by mixing, at the moment of use, a powder containing:

monomorpholinomethylurea ureadimethyl-copra-morpholinomethyl-ureidoethyl ammonium chloride 1 gN-methyl di-[N- (morpholinomethyl)propylureagamine 1 8 pH 2.5 100 ccacetic acid, q.s.p. water N,N'-( morpholinomethylcarbamyl) cystamine 4 gphosphoric acid q.s.p. pH 2.5 water q.s.p. 100 cc The hair is then driedunder a hood for about 30 minutes at a temperature of about 45C.

The hair is then bleached with a conventional oxidizing agent. Thequality of hair which has been thus bleached after being first treatedin accordance with the invention is excellent, under both humid and dryconditions.

EXAMPLE VI:

The first step of a conventional permanent wave is carried out using thefollowing composition:

N-(morpholinomethylcarbamyl)cystamine N,N'-(morpholinomethylcarbamyl)cystamine monoethanolamine, q.s.p.

water q.s.p.

pH 9.5 100 cc.

lasts well, with the hair shiny with a very sofi feel."

EXAMPLE v11;

Natural hair, or hair which has first been bleached is permanentlywaved, using the following self-neutralizing composition:

thioglycolic acid (N-carbamyl-N-morpholinomethylcarbamyhcystamine 7 gammonia q.s.p. pH 9.5

water q.s.p. l cc and then keeping the hair wound up on rollers of smalldiameter, under a cap, for about 15 minutes.

The hair is then rinsed with a 2 percent lactic acid solution and set inconventional manner.

The result is a permanent which imparts excellent cosmetic properties tothe hair, improving its sheen and giving it an agreeable feel.

The hair is springy and the wave lasts well when exposed to the weather.

What is claimed is:

l. A composition for treating human hair comprising a solution in asolvent selected from the group consisting of water and hydroalcoholicsolutions of 0.5 to 12 percent by weight of a polycondensable compoundselected from the group consisting of morpholinomethylurea quaternizedwith methyl iodide and methoxymethylureidomethyl pyridinium chloride.

2. A composition according to claim 1 which also contains an acidcatalyst selected from the group consisting of acetic acid, lactic acid,phosphoric acid, monosodium phosphate and monopotassium phosphate.

3. A composition for treating human hair comprising a solution in asolvent selected frorn the group consisting of water and hydroalcoholicsolutions, of 0.5-1 2 percent by weight of a polycondensable compoundselected from the group consisting of(N-carbamyl-N-morpholinomethylcarbamyl)-cystamine;

N,N-(morpholinomethylcarbamyl)cystarnine;

N-(morpholinomethylcarbamyl)cysteamine;

N-(morpholinomethylcarbamyl)glycine;

(diethyl-methyl-morpholinomethyl-ureidoethyl) ammonium iodide;

(dimethyl-copra-morpholinomethyl-ureidoethyl) ammoniurn chloride;[N-(morpholinomethyl)ethylurea-diethyl-ethylurea]ammonium chloride;methyl-propylurea N-( morpholinoihethyl)propylurea amine;

methyl di-[N-( morpholinomethyl)propylurea] amine;

(N-dimethyl-ethylurea-N'-dimethyl-morpholinomethylureidoethyl)cystaminedichloride;

N-dodecyl-N'-(morpholinomethyl)urea; and

N-octadecyl-N-(morpholinomethyl)urea.

4. The composition according to claim 3 which also contains an acidcatalyst selected from the group consisting of acetic acid, lactic acid,phosphoric acid, monosodium phosphate and monopotassium phosphate.

l i i i UNITED STATES PATENT QFFiCE CERTEMQATR 0F QOERREQWGN 3,67 ,157Dated July 197 Gregoire Kalopissis; Jean-Louis Abegg; Guiliana Gnilardi;and Henri Philippe de Beaulieu Patent No.

Inventor(s) It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

In the heading, add

Claims P y, pplication Luxembourg 5%?5, October 26, 1 6

Signed and sealed this 15th day of January 197L (SEAL) Attest:

EDWARD M. FLETCHER, JR. RENE D.- TEGTD [EYER Attestlng Officer" ActingCommissioner of Patents e g FORM 6 o 10 (10 69) i o i uscoMM-oc nor/m lU S f-(WCNNMINI PNINIINLOHH'! "COO-406d" UNITED STATES PATENT OFFICECERTIFICATE 0F CQRREQTWN Patent No. 3,678,; 157 Dated July 18, 1972Inventor(s) Gregoire Kalopissis et al It is certified that error appearsin the above-identified patent ,and that said Letters Patent are herebycorrected as shown below:

, Column 2, delete lines 70-75.

Column 3, delete lines l-M.

Column 7, line 60, delete "C and insert therefor-methyl-propylurea-N-(morpholinomethyl) propylurea amine".

lines 61-67, delete the structural formula and insert therefor-- (CH-NH-CO-NH-CH N O Signed and sealed this 8th day Of May 1973.

(so-AL) Attest:

Q EDWARD MELETGHElLJR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents FORM PO-IOSO [10-69) USCOMM-DC c0370 Pee 9 U 5 GOVERNMENTPRINTING D'HCI 1 I969 O.\66-l!i

2. A composition according to claim 1 which also contains an acidcatalyst selected from the group consisting of acetic acid, lactic acid,phosphoric acid, monosodium phosphate and monopotassium phosphate.
 3. Acomposition for treating human hair comprising a solution in a solventselected from the group consisting of water and hydroalcoholicsolutions, of 0.5-12 percent by weight of a polycondensable compoundselected from the group consisting of(N-carbamyl-N''-morpholinomethylcarbamyl)-cystamine;N,N''-(morpholinomethylcarbamyl)cystamine;N-(morphoLinomethylcarbamyl)cysteamine;N-(morpholinomethylcarbamyl)glycine;(diethyl-methyl-morpholinomethyl-ureidoethyl) ammonium iodide;(dimethyl-copra-morpholinomethyl-ureidoethyl) ammonium chloride;(N-(morpholinomethyl)ethylurea-diethyl-ethylurea)ammonium chloride;methyl-propylurea N-(morpholinomethyl)propylurea amine; methyldi-(N-(morpholinomethyl)propylurea) amine;(N-dimethyl-ethylurea-N''-dimethyl-morpholinomethylureidoethyl)cystaminedichloride; N-dodecyl-N''-(morpholinomethyl)urea; andN-octadecyl-N''-(morpholinomethyl)urea.
 4. The composition according toclaim 3 which also contains an acid catalyst selected from the groupconsisting of acetic acid, lactic acid, phosphoric acid, monosodiumphosphate and monopotassium phosphate.